Phosphorus compounds



2,894,019 PHOSPHORUS COMPOUNDS Arthur-f Maeder, Therwil, ,Bl, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application January 17, 1958 Serial'No; 711,124"

Claims priority, applicationv Switzerland February 15, 1957' 4 Claims. (Cl; 260-461) The present inventionprovid'esnew organic phosphorus compounds which are.- derived from pentavalent phosphorus and which correspondcto the probable ge eral formula I 7 A1 R: 01 r-iPOH C m (in H 01 1 in which A; and A representorganic radicals which are bound 'to the phosphorus atom directly or through a heteroatom, R represents ;a hydrogen atomor a low molecular alkyl group. and Zrepresents an oxygen'atom or a sulfur atom.

The new compounds may be'prepared by treating an amide of pentavalent phosphorus of the general formula in which A A R and Z have the above meanings, with chloral.

As starting materials of the Formula 2 there come into, consideration, for example, esters of amido-phosphoric acids, of amido-thioephosphoric acids. andof aniido-dithimphosphoric acids. These. compounds corre@ spond more especially tov the general formula Rr-Z Z in which R and R .each represent an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical, R represents a hydrogenatomor a lower alkyl group, and Z represents a sulfunatom, or an oxygen atom. There may be mentioned as examples:

2,894,019 Patented July 7, 1959 2 O O Diethyl-N-ethyl-amidothionophosphate, O: O"Diphenyl-'N-ethylwamidothionophosphate.

There'also come into consideration esters of diamido phosphoric acids,j especiallythose of the general formula in which R R and Z have; the same meanings asin the Formula 3 and R and' R' representfahydrogen, atom ora lower alkyl group; There; may be mentioned as ex amples O-phenyl.-N:N'-dimethyl-diamidophosphate and o-ethyleNzN -dipropyl-diamidophosphate.

Furthermore,--, there come into; consideration N-substituted OfsPhOSPhOIiC and. thiophosphoric' acids, especially those of the formula in whichR R vand Z; have the same meanings as in Formula, 3,.and R' R. andnR'f represent a hydrogen atom or, a lower alk-yl. group. There may be mentioned. as examples;

NzN':N"-triethyl-thionophosphoric acid triamide,

NzN:N"-tripropyl-phosphoric acid triamide,

N :N' N'--triisobuty1-phosphoricl acid triamide,

N-ethyl-N:N t-diisobutyl-thiophosphoric acid' triamide and N-ethyl N:N"-dipheny1phosphoric acid triamide.

There: also: comeinto consideration for use in the processof'the invention .esters'of amido-phosphonic acids and of amido-thiophosphonic acids, especiallylthose of the general formula; V

Rr-Z

in which R R R and Z have the same meanings as in Formula 3; there may bementioned 4-methyl phenyl-O- phenyl-amido-phosphonate; Instead of the mono-amide compounds there may alsobe usedrtheflcorresponding .N- substituted phosphonic l acid diamidesor thiophosphonic acid diamides.

Finally there come intoconsideration-amides of; phosphinic acids and of thiophosphinic acids especially of the general formula in which, R R R and Z have the same meanings as in Formula 3.- There maybe mentioned by way of examples di-(A-methylphenyl).-thionophosphinic acid amide.

The reaction. between the vcomponents may advantageously bev carried outwith the useof equimolecular proportions. The. components may be mixed directly or the reaction may, be carried outin thepresence of inert solvents as, for example, aliphatic or aromatic hydrocarbons or their halogen-derivatives for example, benzene, toluene, hexane, chlorobenzene, chloroform or carbon tetrachloride. Further, there may be used as solvents etherlike compounds as, for example, dioxane, or tetrahydrofurane and finally saturated amides 'which contain on the amide nitrogen atom no hydrogen atom as, for example, dimethyl formamide. The reaction may advantageously be carried. out at moderately raised temperatures, for example, 30 to 100 C., and preferably in the presence of basic catalysts, especially tertiary bases, for example, tri'ethylamine, pyridine and dimethyl aniline.

The new condensation products can probably be denoted as N-(beta-trichloro-alpha-hydroxyethyl)-derivatives of the amide of pentavalentphosphorus used in the condensation and are generally obtained in the form of good crystalline bodies. They may be used for different purposes in industry, for example, as pest-combating agents, flame-protecting agents, textile assistants, plasticisers, lubricant additives and intermediate products.

The following examples illustrate the invention the parts being by weight unless otherwise. indicated, and the relationship between parts by weight and parts by volume being the same as that between the kilogram and the liter:

Example 1 22.2 parts of O:O'-di-(beta-chlorethyl)-amidophosphate were mixed with 15 parts of chloral with exclusion of moisture. In order to accelerate the condensation reaction there was added to. this mixture 0.1 part of triethylamine and the mixture was heated on the water bath for 2 /2 hours at 65 to 75" C. The crude condensation product (36.2 parts) was now dissolved in 25 parts by volume of methanol and transferred to a separating funnel. Upon addition of water an oil separated, from which 21 parts of .the condensation'productcrystallized at once.. The separated crystals, after drying, were recrystallized from 5 times their weight of carbon tetrachloride; they had a melting point of 91-92 C. From the above described methanolic-aqueous, motherliquor there separated after standing for several hours a further quantity of the same condensation product in the form of fine, felted, needle aggregates. The product was readily soluble in methanol and ethanol, as well as in ethyl acetate and acetone, but it was only slightly todifiicultly soluble in cold benzene and carbon tetrachloride. In the latter solvent the product was soluble at raised temperatures.

The product so obtained had the empiricalformula C H O NPCI and gave the following analysis.

Calculated, Found,

percent percent The product had the following probable constitutional formula: I

ClCHaCHa-O 2 01 1 r-Nn-on-o-ol moment-'0 b n 01 Example 2 Calculated, Found,

percent percent The subtances had probably the following constitution:

15.8 parts of 'di-(para-chlorophenyl)-phosphoric acid amide, 15 parts by volume of dioxane and 15 parts of anhydrous chloral were dissolved while heating gently; The solution was then heated for one hour at 85 C.

and for three hours at 90- C. After distilling off the dioxane in vacuo, the residue (23.0 parts) was dissolved in 100 parts by volume of methylene chloride. After cooling, the condensation product was obtained the form'of fine needles meltingat-142 143 C. f?

The chlorine'.analysi sgave the-following values: 'Cl calculated 38.09%. Found 38.29%." g i Y The substance had probably the following 'cons tit tion:

;. GIG-0' When tomato or celery-plants are sprayed with a liquor containing 0.1 percent of the above compound, they are protected against Alternaria solani, Septaria apii and Phytophtora infestans.

Example 4 h 2 parts of the reaction product from O:O.'-'di -(betachloroethyl)-amidophosphate and chloral, obtained as described in Example 1, were dissolved in 4 parts byvol ume of ethanol and 2 parts of water were then added. The pH was adjusted to 4' by the addition of a little formic acid, and a solution of 1 part of a condensation product,

which had a limited solubility in water, from 1 mol of melamine and about -3 mols' of formaldehyde in 1 part of water was added.

With the resulting bath a blue cotton overall-material was impregnated at about 40 C. on a -foulard, dried, hardened for 5 minutes at C. and then rinsed; The fabric so treated showed very good non-smouldering properties and resistance to flames; the handle was only slightly stiffer and the tint remained unchanged.

What is claimed is: 1 i 1. The compound of theformula v ClCHaCHa-O i 261 r -NH :H- o-o1" clement-0 o on jc f' 2. The compound of the formula {'f C2H60. 01 f];

' U V 1 "'Nri-o11 o o1' CgHs-O i) l H. Cl 3. The compound of the formula 1 4. An organic phosphorus compound of the formula in which A and A each represents a member selected from the group consisting of lower aliphatic radicals and aromatic radicals with a single 6-membered ring.

No references cited.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,894,019 July 7, 1959 Arthur Maeder It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 60 to 63, the formula should appear as shown below instead of as in the patent:

Attest: KARL H. AXLINE, Y ROBERT C. WATSON, Attes ting 07ficer. fl nmiwioner of Patents.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,894,019 July 7 1959 Arthur Maeder It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 60 to 63, the formula should appear as shown below instead of as in the patent:

\P-NHR Re Signed and sealed this 15th day of December 1959.

[SEAL] Attest:

RL H. AXLINE, ROBERT C. WATSON, Attestz'ng Ofiaer. Commissioner of Patents. 

1. A COMPOUND OF THE FORMULA 